Phosphorothiolothionate derivatives of cyanoacrylates



United States Patent 3,106,566 PHOSPHGROTHIOLOTHIONATE DERIVA'HVES 0FCYANOACRYLATES Marvin A. McCall and Richard L. McConneil, Kingsport,

Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., acorporation of New Jersey No Drawing. Filed Feb. 9, 1962, Ser. No.17241336 6 Claims. (Cl. 260-3322) This invention relates to neworganophosphorus compounds and to their method of preparation. In aspecific aspect this invention relates to the preparation of neworganophosphorus compounds by the reaction of dia=llylphosphorothiolothionates with a-cyanoacrylates and to the products ofthis process.

This is a continuation-impart of our copending application Serial No.705,800, filed December 30, 1957, now abandoned.

Organophosphorus compounds have evidenced marked utility and importancein many fields. For example, they have been employed as insecticides,fungicides, pesticides and in related uses. Consequently, it is ofconsiderable importance to discover new and useful organophosphoruscompounds and to have a new process for the production oforganoph-osphorus compounds. Therefore, it is an object of thisinvention to provide new and useful organophosphorus compounds. It isanother object of this inventionto provide a novel method for preparingthe new and useful organophosphorus compounds. It is still anotherobject of this invention to provide new and valuable insecticides thatcan be used in various insecticidal compositions.

In accordance with this invention it has been found that neworganophosphorus compounds, useful as insecticides, can be prepared byreacting dialkyl phosphorothiolothionates wit-h a-cyanoacrylates. Thenew products of this invention have the structural formula:

wherein R and R are selected from the group consisting of lower alkylradicals and chlorinated lower alkyl radicals (chloroethyl,chloropropyl, tricliloroethyl, and the like), R is selected from thegroup consisting of hydrogen and low alkyl, R, is selected from thegroup consisting 'of lower alkoxy, nit-rophenyl (ortho-, meta-, para-),ch lorophenyl (ortho-, meta-, para-), furyl, thienyl and pyridyl, and Ris selected from the group consisting of lower alkyl and phenyl.

The compounds of this invention are prepared by reacting a dialkylphosphorothiolothionate having the struc tural formula:

PSH

3,106,566 Patented Oct. 8, 1963 ice with an a-cyanoacrylate having thestructural formula:

wherein R R R R and R are as defined above.

In the practice of this invention we prefer to add one of the reactantsgradually to a reactor containing the other reactant. For example, thecyanoacrylate can be added gradually to a reactor containing the dialkylphosphorothiolothionate. Alternatively however, the reverse procedure ofaddition of reactants can be used and the dialkylphosphorothiolothionate can be added to a reactor containing thecyanoacry-late. When the cyanoacrylate polymerizes readily, it ispreferred to add this reactant gradually to thephosphoro-thiolothionate. The substitute-d cyanoacrylates, such asbenzylidenecyanoacetate and the al kyl idenecyanoacetates, do notpolymerize readily, and when these reactants are used either method ofaddition is suitable. Normally it is desirable to employ a reactorprovided with adequate means of agitation and, since the reaction isquite exothermic, it is also desirable to employ a reactor that isprovided with adequate coo-ling means.

The operable temperature range for the reaction is generally from 25 to150 C. and the preferred temperature range is from 25 to C. However, itwill be realized that in some instances temperatures outside this rangecan be employed. The reaction time usually varies from 0.5 to 8 hours,but longer and shorter reaction periods are sometimes used. Normally itis unnecessary to employ a catalyst for the reaction since thediallrylphosphorothiolothionate will react with the cyanoacrylate in theabsence of a catalyst. If it is considered desirable to employ acatalyst, there are certain catalysts that can be used. For example, thetertiary amines, such as triethyl amine, and the like, are quitesuitable.

Ordinarily, it is not necessary to employ a solvent for the reaction butin some instances solvents are desirable. Among the solvents that can beused are normally liquid aliphatic and aromatic hydrocarbons such aspentane, heptane, octanc, benzene, toluene, the xylenes and the like,chlorinated derivatives of the above-mentioned hydrocarbons as well asthe common ether and ester solvents. It is preferable to carry out thereaction using equiniolar quantities of the reactants. However, theratio of reactants can be varied rather widely.

The dialkylphosphonothioiothionates that are used in our invention canbe prepared by the known reaction of 4 moles of an aliphatic alcoholwith one mole of phosphorus pentasulfide. The alkyl and aryla-cyanoacrylates can be made by depclymerizing a polymeric ester ofacyanoacrylic acid by heating the polymer in a tertiary ester ofphosphoric acid at a temperature above the melting point of the polymerand at a pressure below 15 mm. of mercury as described in U.S.2,756,251. The ,B-substituted acrylates can be prepared by reactingalkyl or aryl cyanoacetic acid ester with the appropriate aldehyde by aprocedure similar to that described in Organic Syntheses, vol. 25, pages42 and 46 (1945), published by John Wiley and Sons, Inc.

The following examples are illustrative of the compounds Within thescope of this invention, their method of preparation and their utilityas insecticides.

Example 1.-Metlzyl 2-Cyan0-3-(o Nitrophenyl)-3-(O,O-Dimetlzylphosphorothiolothiorzo)Propiorzate CN This compound was made bythe addition of methyl (o-nitro'oenzylidene)-cyanoacetate (0.1 mole)dissolved in benzene to 0,0-dimethyl phosphorothiolothionate withstirring. A few drops of triethylamine was added as r 0 catalyst. Afterthe addition was complete, the reaction was heated on a steam bath for 1hour to complete the reaction. The product was obtained as a dark oilafter removing the benzene solvent under vacuum.

Example 2.Methyl 2-Cyan0-3-(p-Clzloroplzenyl)-3-(O,O-Diethylphosphorotlziolotlziono)Propionate This compound was made bythe addition of methyl (pchlorobenzylideue)-cyanoacetate (0.1 mole) incarbon tetrachloride solvent to 0,0-diethyl phosphorothiolothionate (0.1mole) with stirring. A small amount of triethylamine was used ascatalyst. The dark oily product was obtained after the solvent wasremoved under reduced pressure.

Example 3.-Mezhyl 2-Cyan0-3-(2-Furyl)-3-(0,0-DiethylP/zosplzorothfolothiono)Propionale This compound was prepared by thesame general procedure given in Example 1 except that benzene was usedas a solvent and triethylamine as catalyst. The reactants were methylZ-furfurylidenecyanoacetate (0.1 mole) and O,G-diethylphosphorothiolothionate (0.1 mole). The product was obtained as an oilafter removing the solvent under reduced pressure.

.cample 4.-Butyl 2-Cyan0-3-(2-Thienyl)-3-(0,0-DiethylPhosphororhiolothiono)Propionate CN rllu-orr-ooooila N SP(S)(CH:)2 Thiscompound was prepared from methyl 2-(2-pyridyl)methylenecyanoacetate and0,0-dimethyl phosphorothiolothionate by the same general procedure givenin Example 1 except that benzene was used as solvent and triethylamineas catalyst for this reaction. The dark oily product had excellentpesticidul properties.

4 Example 6.-Metlzyl2-Cyan0-3-ElIr0:cy-3-(0,0-Dictlzylphosp/zorotlzioloth0110)BuzyraleClIs-C-CH (C2U5O)2P (S) S COUCH:

This compound was prepared by the addition of methyl2-cyano-3-etho-:tycrotenate to 0,0-diethyl phosphorothiolothionateaccording to the procedure of Example 1.

Example 7.Use 0 Compounds as Insecticides Tests against mites werecarried out in the following manner. Acetone solutions containing 1% ofthe candidate compounds were prepared and diluted with water to givesolutions of the desired concentration for testing. Two heavily infestedbean leaves containing adult twospottccl mites (Terranychus bimaculatllsHarvey) were carefully dipped in the above solutions and dried in agentle air stream. The leaves were then placed on damp paper toweling inpetri dishes and observed after 24 hours for mortality among the adultmites. It should be noted that tests using acetone-water solutions(containing none of the toxicant) kill none of the mites.

Conccn- Percent tration 01 Kill mxicant Mites in ppm.

1. Methyl 2-Cyano-3-(o-nltrophcnyl)-3 (0. O-(li- 100 100 ethylphosphorothiolothlone) propionate (Ex. 30 92 1). 10 89 2. Methyl2-Cyano'-(2-pyrltlyl)-3-(O. O- liethyl 100 100 phosphorothlolothiono)propionutc (Ex. 5). 30 95 10 90 The compounds of Examples 2, 3, 4, and 6were similarly effective when used in the above tests.

We claim:

1. The organophosphorus compounds having the structural formula:

3. As a composition of matter, butyl 2-cyano-3-(2- thienyl-3-(0,0-diethyl phosphorothiolothiono) propionate having the formula:

4-. As a composition of matter, methyl 2-cyano-3- 3, 1 (3 G, 5 6 6 5 eethoXy-3- 0,0-d'iethy1 phosphorothiolothiono butyrate having theformula: propionate having the formula:

References Cited in the file of this patent UNITED STATES PATENTS COOCH:

5. As a composition of matter, methyl 2-cyano-3-(2-furyl)-3-(0,0-diethyl phosphorothiolothiono)propionate 0 having formula:2,826,530 Eddy et a1 Mar. 11, 1958 2,889,330 Baker et a1 June 2, 1959 I(3N 2,947,662 Fusco et a1 Aug. 2, 1960 I 2,957,007 McCall et a1. OCL.18, 1960 15 OTHER REFERENCES 0 SP(S) (0 0211 Chemical Abstracts, volume4-8, pages 556i, 557a, 1954.

6. As a composition of matter, methyl 2-cyano-3-(p- Chemical Abstracts,volume 48, page 6639, 1954.

chlorophe-nyl) 3 (0,0-diethylphosphorothiolo-thiono)-

1. THE ORGANOPHOSPHORUS COMPOUNDS HAVING THE STRUCTURAL FORMULA:
 3. AS ACOMPOSITION OF MATTER, BUTYL 2-CYANO-3-(2THIENYL)-3-(O,O-DIETHYLPHOSPHOROTHIOLOTHIONO)PROPIO NATE HAVING THE FORMULA: